N, n&#39;-alkylene-bis-1-aziridine carboximides as insects sterilants



United States Patent 3,208,905 N,N-ALKYLENE-BIS-l-AZIRIDINE CARBOXIM- IDES AS INSETS STERILANTS Samuel S. Ristich, East Brunswick, and Barbara Stearns,

New Brunswick, N.J., assignors to Olin Mathiesou Chemical Corporation, New York, N.Y., a corporation of Virginia No Drawing. Filed Mar. 12, 1963, Ser. No. 264,689 4 Claims. (Cl. 16733) This invention relates to new compositions of matter and more particularly, to new compositions of matter useful in the combating of certain harmful insects.

The insect combating compositions of this invention comprise a compound of the formula R1 R1 o as wherein R is alkylene, either straight or branch chained of from 2 to 21 carbon atoms, and each R is the same and may be hydrogen or lower alkyl, as the principal active ingredient, said compound dispersed in a substantial amount of a suitable extending agent.

In the preferable embodiment of this invention R is an alkylene, either straight or branch chained of from 4 to 12 carbon atoms and each R is hydrogen; and most preferably, R is an alkylene, either straight or branch chained of from 6 to 10 carbon atoms and each R is hydrogen.

In this disclosure and in the claims appended thereto, the term, dispersed is used in its widest possible sense. When it is said that the compounds of this invention are dispersed it means that the particles may be molecular in size and held in true solution in a suitable solvent. It means further, that the particle may be colloidal in size and dispersed through a liquid phase in the form of suspension or emulsions or in the form of particles held in suspension by wetting agents. It also includes particles which are dispersed in a semi-solid viscous carrier such as petrolatum or soap in which they may be actually dissolved in the carrier or held in suspension in the carrier with the aid of suitable emulsifying or wetting agents. The term dispersed also means that the particles may be mixed with and spread throughout a solid carrier so that the mixture is in the form of powder or dust. The term dispersed also includes mixtures which are suitable for use as aerosols including solutions, suspensions or emulsions of the agents of this invention in a carrier such as Freon which boils below room temperature at ordinary pressure.

The term extending agent as used in this disclosure and in the appended claims, includes any and all of those agents in which the compounds of the instant invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of dust and powders.

It has been found that the compounds of this invention are active when dispersed in an extending agent at concentrations of .005 by weight or even lower. This concentration is effective when the dispersing agent is a liquid but it is preferred to use more concentrated mixtures when the dispersing agent is a semi-solid or a solid. This is because liquid dispersions which are, of course, suitable for use as sprays give a more intimate contact with the insects than the solid dispersions and, therefore, lower concentrations are more effective with liquid dispersions.

There are a number of solvents which can be utilized for the preparation of solutions, suspensions or emulsions of the compounds of this invention. High boiling oils of ice vegetable origin such as castor oil or olive oil have been found to be suitable. Low boiling, more volatile solvents such as acetone, alcohols, such as methanol and ethanol, benzene, toluene and the like are also useful. For certain applications it may be advantageous to resort to mixtures of solvents.

If the active agents are to be applied as aerosols, it is convenient to dissolve them in a suitable solvent and to disperse the resulting solution in a liquid such as Freon which boils below room temperature. For such applications it is better to employ true solutions of the active agent although it is possible to employ suspensions or emulsions of the active agent.

The agents of this invention are often dispersed either in the form of emulsions or suspensions, in an inert carrier with the aid of a capillary active substance. Such capillary substances may be anion-active, cation-active or non-ionizing. There may be mentioned by way of example, natural or synthetic soaps, Turkey-red oil, fatty alcohol sulfonates, esters of fatty acids and the like. Other examples include high molecular weight quaternary ammonium compounds as well as condensation products of ethylene and propylene oxide with monohydric and polyhydn'c alcohols.

For use as a powder or dust the active ingredients of this invention may be mixed with any of a number of extending agents either organic or inorganic in nature which are suitable for the manufacture of pulverulent preparations. In addition to mixing the ingredients directly the active compounds of this invention may first be dissolved in a suitable solvent and the dry extending agents may be treated with the resulting solution so that after the solvent evaporates off the active ingredient is effectively coated on the surface of the extending agent. The extending agents which may be employed include, for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, calcined magnesia, boric acid and others. Materials of vegetable origin such as powdered cork, powdered wood and powdered walnut shells are also useful. These mixtures may be used in the dry form or, by the addition of wetting agents, the dry powder can be rendered wettable by water so as to obtain stable aqueous dispersions suitable for use as sprays.

For special purposes the agents of this invention can be worked into the form of a paste or an ointment by the use of such semi-solid extending agents as soap or petroleum jelly with or without the aid of solubility promoters and/ or dispersing agents.

It has been found that the most satisfactory results are obtained when the active ingredient of this invention is present in an amount of from .005 to 5.0% by weight of the final composition, and optimally, in an amount of from .O1% to 2.0% by weight of the final product.

The compositions of this invention are employed as insecticides in a particular manner. Unlike the usual insecticide formulations, these compositions are not employed to kill the insect treated, but rather the compositions of this invention are useful as insect sterilizing agents. The compositions are useful in combatting by sterilization such insects as houseflies, fruit flies, flesh flies, latrine flies, mosquitoes, boll weevils, and the like, and are applied for such purposes in the environment of the insect or on surfaces on which it may light, including plants attacked by the pest. Also, the compositions may be employed in conjunction with attractants for the particular insect being treated, for example, it may be mixed with or applied to such attractants or baits as sucrose, glucose, powdered egg, powdered milk, yellow corn grits, quincy granulars, pumice granulars and other like materials.

Generally, the active ingredient of the compositions of this invention is prepared by a process which comprises -rea-cting an alkylene di-isocyanate, e.g

nate, propylene diisocyanate, butylene d-iisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, trimethylpentylene diisocyanate, 2-methyl butylene-diisocyanate and other like compounds, with ethylene imine. While the reaction can be carried out in any suitable solvent medium, in the preferred practice of this invention, the solvent medium employed is acetone.

. The following examples are for the purposes of illustrating the invention and should not be considered limitat-ive thereof.

EXAMPLE 1 N,N-decamethylene-bis-1-aziridine carboxamide 3.4 g. of ethyleneim-ine dissolved in ml. of acetone is added to an ice-cooled solution of 8.8 g. of decamethylene diisocyanate in 40 ml. of acetone. The mixture is stirred for two hours and then allowed to stand overnight. At the end of this period, the mixture is filtered to provide N,N'-decamethylene-bis-l-aziridine carboxamide in 95% ethylene diisocyalents either alone or as a yield. Upon recrystallization the purified product has a melting point of 112-113 C.

EXAMPLE 2 N,N'-hexamethylene-bis-I-aziridine carboxwmide Following the procedure set forth in Example 1 but substituting an equivalent amount of hexa-rnethylene diisocyanate for decamethylene diisocyanate, there is obtained N,N'-hexamethylene-bis-l-aziridine carboxamide.

EXAMPLE 3 N,N-hexamethylene-bis-1-(Z-methylaziridine) carboxamide 11.4 grarns of 2-methylaziridine dissolved in 20 ml. of acetone is added to an ice cooled solution of 16.8 grams of hexamethylene diisocyanate in 100 ml. of acetone. The mixture is stirred for two hours at 5 and then allowed to warm to room temperature. After 24 hours, the solution is concentrated and the desired N,-N'-hexamethylenebis1-(2-methylaziridine)carboxamide which precipitates out is isolated by filtration.

EXAMPLE 4 g. of N,N'-decamethylene bis-aziridine carboxamide is dissolved in 150 vmls. of ethanol. The resulting solution is then placed in a vessel containing 72 g. of finely divided kaolinic clay and 3 g. of Tween 20, a surfactant is introduced-and the ingredients are thoroughly mixed, the solvent is driven 0E and the resultant dry coated kaolinic clay is dispersed in 490-0 cc. of water. This final suspension maybe sprayed directly on theareas to be treated to give the desired results.

EXAMPLE 5 Two g. of N,N'-hexamethylene-bis-l-aziridine carboxamide is dissolved in 15 ml. of acetonide. To this solution is added 5 g. of sucrose and 93 g. of quincy granules and theresultant mixture is thoroughly stirred and mixed. The acetone is then driven ofi leaving a resultant powdered solid having impregnated thereon a suflicient amount of N,N'-hexamethylene-bis-l-aziridine carboxamide to accomplish the desired results. The resultant powder may be spread and distributed in those areas in which the insects sought to be sterilized are prevalent.

EXAMPLE 6 -(A) A composition of the following formula is prepared:

Grams described in Example The N,N'-deca-methylene-bis-l-aziridine carboxamide is dissolved in a solution of the benzene and low viscosity petroleum oil.

(B) The foregoing composition is then introduced into a pressure packaged disperser of known type along with 82 g. of a suitable propellant such as a mixture of 50 parts trichloromonofluoro-methane (Freon 11, Dupont) and 50 parts dichlorodifiuoromethane or similar propelmixture. The pressure pack is capped with a suitable value. Suitable dispersers are disclosed, for example, in US. Patent No. 1,892,750 dated January 3, 1933 and in US. Patent No. 2,440,915 dated May 4, 1948. I

EXAMPLE 7 (A) A composition of the following formula is prepared:

' Grams N,N-hexamethylene-bis-1-(Z-methylaziridine)carboxamide 0.10 Polyethylene (mol. weight, 21000) 0.95 Mineral oil 18.05

A polyethylene mineral oil dispersion is prepared as -1 of US. Patent No. 2,628,187, issued February 10, 1953 and the N,N'-hexamethylene-bis- 1-(2-methylaziridine) carboxamide is incorporated therein.

This invention may be variously otherwise embodied within the scope of the appended claims.

What is claimed is:

1. The method of sterilizing insects which comprises contacting said insects with a composition comprising as its sterilizing agent, from about 0.005% to about 5.0% by weight of a compound of the formula wherein n is an integer of from two to twenty-one and each R is the same and is selected from the group consisting of hydrogen and lower alkyl, said sterilizing agent dispersed in an extending agent.

2. The method of claim 1, wherein the sterilizing agent is N,N'decamethylene-bis-l-aziridine carboxamide.

I 3. The method of claim 1, wherein the sterilizing agent is N,N'-hexamethylene-bis-l-aziridine carboxamide.

4. The method of claim 1, wherein the sterilizing agent is N,N-hexamethylene-bis-1-(2-methylaziridine)carboxamide.

References Cited by the Examiner UNITED STATES PATENTS 2,390,165 12/45 Orthner et al 260-239 2,950,197 8/60 Allen et al 260-239 OTHER REFERENCES Borkovec: Science, vol. 137, pages 1034-1036, September 1962.

Labrecquer: Journal of Economic Entomology, vol. 54, No. 4, pages 684-689, August 1961.

JULIAN s. LEVITT, Primary Examiner. FRANK CACCIAPAGLLA, JR., Examiner. 

1. THE METHOD OF STERILIZING INSECTS WHICH COMPRISES CONTACTING SAID INSECTS WITH A COMPOSITION COMPRISING AS ITS STERILIZING AGENT, FROM ABOUT 0.005% TO ABOUT 5.0% BY WEIGHT OF A COMPOUND OF THE FORMULA 